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2 Atomic Structure

LOOKING AHEAD
This chapter deals with the structure of the atom, particularly with
the subatomic particle called the electron. Today’s model of the
atom—the quantum mechanical model—evolved from the work
of many scientists and provides a basis for understanding the
behavior of elements and the nature of bonds between atoms.

When you have completed this chapter, you should be able to:
■ Describe the general structure of the atom.
■ Define nucleon, atomic number, atomic mass, isotope, gram-
atomic mass, mass number, orbital, sublevel, ionization energy,
electron affinity, and electronegativity.
■ Explain some of the early significant experiments that led to
our present understanding of the atom.
■ Relate the experimental results from atomic emission spec-
troscopy to Bohr’s model for electrons in atoms.
■ State two key differences between the Bohr model and the
quantum mechanical model.
■ Diagram the electron configuration of an atom.
■ Determine the number of valence electrons of an atom on the
basis of electron configuration.

65
Early Models of the Atom
The idea that matter is composed of tiny, indivisible particles was
proposed by Democritus, a Greek philosopher, about 2500 years
ago. In fact, the word “atom” comes from a Greek word meaning
“indivisible.” However, the ancient concept of an atom was very
different from the modern one. Democritus believed that all atoms
were exactly the same. What made one substance different from
another was the way the atoms were linked together. The Greek
philosophers did not do experiments to test their beliefs, and the
existence of atoms remained an unproved and unpopular concept
until just about 200 years ago. In 1803, on the basis of a great deal
of experimental evidence then available to him, an Englishman
named John Dalton proposed the first modern atomic theory.
Dalton’s theory included the following statements:
1. Elements are composed of tiny, indivisible particles, called
atoms.
2. All atoms within a given element are identical.
3. Atoms of different elements are different.
4. During a chemical reaction, atoms can be neither created nor
destroyed; they are simply rearranged.
As we learn more about atoms, we will see that the first two of
these statements are not entirely accurate. However, Dalton’s
atomic theory gave scientists a far better view of the nature of
matter than had been proposed previously. Dalton is often called
“The Father of Atomic Theory.”
Dalton believed that no particles smaller than atoms existed.
Evidence that there are smaller, or subatomic particles came from
the study of electricity.

Static Electricity
We have all occasionally experienced the mild electric shock
that results from walking across a carpet and then touching a metal
object. If you pull a woolen sweater over your head on a cold, dry
day, you may hear a crackling sound and, in a dark room, may
even see the sparks produced by static electricity. In the 1750s,
Benjamin Franklin studied the charge that develops when various
objects are rubbed against wool or silk. He concluded that there are

66 | Chapter 2: Atomic Structure


just two types of charge, which he called positive () and negative
(). Objects with like charges repel each other, while objects with
opposite charges attract each other. The cause of these static
charges, however, remained a mystery for another hundred years.

The Cathode Ray Tube


In the nineteenth century, scientists discovered how to gener-
ate large amounts of electricity. They observed that when most of
the air is pumped out of a glass tube, the remaining gas will glow
when a sufficient amount of electricity is applied to it. Chemists
discovered that by placing different gases in the tubes, they could
produce different colors of light; the orange glow of neon lights is
produced this way. Certain solids, such as zinc sulfide, also will
glow in a vacuum tube when electricity is passed through them.
By coating a metal with zinc sulfide, and using a narrow slit to
focus the resulting beam of light, the scientists were able to con-
clude that the beam was moving from the negative terminal to
the positive terminal. The negative terminal of a battery is called
a cathode, and so the beam of light became known as a cathode
ray. Cathode ray tubes of the type shown in Figure 2-1 were used
to determine the nature of these cathode rays.

The electron On the basis of his experiments with cathode ray


tubes, the British scientist J.J. Thomson concluded that the cathode

Narrow slit
Cathode Anode
– +

(–) (+)

Power source

Figure 2-1 Cathode ray tube

Early Models of the Atom | 67


ray was actually a stream of negatively charged particles. He named
these particles electrons. Thomson found that all elements con-
tained identical electrons, and later experiments indicated that the
mass of an electron is far smaller (more than 1800 times) than the
mass of the lightest atom. Since atoms are neutral, and contain neg-
ative electrons, they must also contain a source of positive charge.

The nucleus Thomson had found a negative subatomic particle,


the electron. With no positive particle having been discovered, he
proposed what became known as the “plum pudding” model of
the atom. In this model, negatively charged electrons are imbed-
ded in a positively charged “pudding” like small pieces of fruit.
(See Figure 2-2) In 1909, a team of scientists led by Ernest
Rutherford designed an experiment to test this model.
Rutherford’s experiment made use of polonium, a radioactive
element that gives off positively charged alpha particles. A stream
of these particles was allowed to strike a very thin sheet of gold or
copper. Behind the metal foil, there was a fluorescent screen.
A diagram of the effects Rutherford and his co-workers
observed is shown in Figure 2-3. Most of the alpha particles
passed through the metal foil with very little interference. Each
time one of these alpha particles hit the fluorescent screen, a flash
of light was given off. But a few particles did not pass directly
through the foil. They were deflected, or turned aside from their
paths. Most of the deflections were at small angles, but some were
at relatively large angles. About one alpha particle in 20,000 was
deflected through an angle greater than 90°. In effect, some of the

Cloud of positive
charge

Electrons

Figure 2-2 The “Plum Pudding” model

68 | Chapter 2: Atomic Structure


Source of alpha Some particles Some alpha Most particles
particles (embedded bounce back particles are pass straight
in a lead block to absorb scattered through foil
most of the radiation)

Beam of Coated screen Thin gold


alpha particles to detect scattered foil
alpha particles

Figure 2-3 Rutherford’s experiment

particles seemed to move back toward the polonium from which


they had been given off. Rutherford and his co-workers reacted
with surprise when they observed these large deflections.
Rutherford is quoted as saying, “It was almost as incredible as if
you fired a 15-inch shell at a piece of tissue paper and it came
back and hit you.”
To better understand Rutherford’s experiment, visualize yourself
blindfolded, standing in front of a fence. You do not know what
kind of fence it is, so to find out, you start throwing small pebbles at
the fence. Most of the time you hear nothing at all. Occasionally,
you hear a faint “clink” as the pebble seems to contact something
on its way through the fence. And then, on very rare occasions, the
pebble strikes something solidly, and bounces back at you. What
would you expect the fence to look like? (See Figure 2-4)
Rutherford concluded that like our fence, atoms consist
mostly of empty space. However, they also contain a tiny, massive
center, which he called the nucleus. The nucleus is positively

Figure 2-4 One type of fence

Early Models of the Atom | 69


charged, and although extremely small, it contains most of the
mass of the atom.
The experiments of Thomson, Rutherford, and many others
led to our modern view of the general structure of the atom.

The General Structure of an Atom


An atom, you will recall, is the smallest part of an element that
retains the properties of the element. Atoms, in turn, are made up
of smaller parts, or particles. These fundamental particles of an
atom include protons, electrons, and neutrons. There are other
atomic particles also, but they will not be discussed in this chapter.
The proton is a particle with a positive electrical charge. It is
assigned a unit charge of 1. The mass of a proton is almost
exactly the mass of a hydrogen atom.
The electron is a negatively charged particle with a unit
charge of 1. The electron is the smallest of the three fundamen-
tal particles. It has a mass only 1/1837 the mass of a proton.
The neutron has no charge—it is an electrically neutral parti-
cle. The mass of a neutron is only very slightly greater than the
mass of a proton. For all practical purposes, the mass of a neutron
and the mass of a proton are considered equal.
Atoms are electrically neutral. This means that the number
of protons in an atom must be equal to the number of electrons.
Recall, too, that the number of protons (and of electrons) in an
atom is different for each of the elements. The number of
protons in an atom is called the atomic number. An atomic
number describes a particular atom and the element of which it
is a part.
Together, protons and neutrons make up nearly the entire
mass of an atom. The sum of these two particles—protons and
neutrons—is called the mass number of an atom. The mass of
the electron is so small that it is usually ignored when the mass of
an atom is considered. This is true even when an atom contains
100 or more electrons.
Protons and neutrons are also called nucleons. They
are located in the center of the atom, in the region called the
nucleus. The electrons are located outside the nucleus. Each kind
of atom has a specific arrangement of electrons.

70 | Chapter 2: Atomic Structure


The Size of Atoms
Although the nucleus may have more than 100 protons and
more than 150 neutrons, the nucleus is only a very small region of
the atom. An average atom may have a radius of about 1  108
centimeter (cm), one-hundred millionth of a centimeter. The radius
of its nucleus is about 1  1013 cm (one-ten trillionth of a cen-
timeter). Thus the radius of the whole atom is 105 (one hundred
thousand) times greater than the radius of the nucleus of the atom.
Both the atom and the nucleus can be thought of as spheres.
The volume of the whole atom can be compared with the volume
of the nucleus alone, because the volume of a sphere is propor-
tional to the cube of its radius. The ratio of the volume of an
atom to the volume of its nucleus is
s1 3 1028 cmd3 1 3 10224 cm3
  1  1015
s1 3 10213 cmd3 1 3 10239 cm3
The volume of an atom is about 1015 (one quadrillion) times
larger than the volume of its nucleus. Nearly the entire mass of an
atom is packed into the tiny nucleus.

Atomic Number
Rutherford and his co-workers repeated the “gold leaf” experi-
ment many times, using different metals to deflect alpha particles.
They concluded that each element has a characteristic number of
positive charges in its nucleus. This conclusion was later con-
firmed by the English physicist Henry Moseley. Moseley used the
term atomic number to refer to the number of positive charges in
the nucleus of an atom. Since each proton carries one positive
charge, the atomic number represents the number of protons in
the nucleus of an atom. In a neutral atom, the atomic number also
equals the number of electrons outside the nucleus, since the
charge of the electrons balances the positive charge of the nucleus.
The atomic number of an element never changes. If the number
of protons in a nucleus changes, the element changes into another
element with a different atomic number. As long as the number of
protons does not change, the element remains the same.

Atomic Mass
As you know, atoms are very small in size. The actual mass of
any atom is also very small. For example, the mass in grams of an

The General Structure of an Atom | 71


oxygen atom is approximately 2.67  1023 gram. To avoid using
such small numbers, an arbitrary scale for the mass of elements
has been developed. On the scale, the mass of the elements is
given in units called atomic mass units. One atomic mass unit
1
(amu) is equal to 12 the mass of an atom of the most abundant
form of carbon. This form of carbon (carbon-12) is assigned a rel-
ative atomic mass of exactly 12 amu. Therefore, an atom of an
element with exactly twice the mass of a carbon-12 atom has a
mass of 24 amu, and one with half the mass of carbon-12 has a
mass of 6 amu. You should remember that atomic mass units are
relative, or comparative, masses, the standard being carbon-12.
One atomic mass unit is very close to the mass of a proton or
neutron. In practice, therefore, both the neutron and the proton
are given a mass of 1 amu. Thus it is possible to describe the mass
of an atom, or the mass number, as the sum of the protons and
neutrons in its nucleus.

Molecular Mass
The mass of a molecule (the molecular mass) is the sum of
the atomic masses of all the atoms in the molecule. Thus the
molecular mass of hydrogen is 2 amu, because a molecule of
hydrogen consists of two atoms, each of which has an atomic
mass of 1 amu. The molecular mass of water (H2O) is 18 amu.
H  2  1 amu  2
O  1  16 amu  16
H2O  18 amu
Since atomic mass units are relative masses, molecular masses are
relative also.

PRACTICE
2.1 How did Thomson’s view of the atom differ from that of
Democritus?
2.2 When alpha particles are shot at a thin gold leaf, only one
particle in about 20,000 bounces back. How would
Rutherford explain this observation?

72 | Chapter 2: Atomic Structure


2.3 What is the atomic number of a neutral atom that con-
tains 14 electrons? Explain your answer.
2.4 A certain atom contains 6 protons, 8 neutrons, and 6 elec-
trons. How many and which of these particles are in the
nucleus of this atom?

Atomic Mass and Isotopes


Look up the atomic mass of chlorine in a reference table, such
as the one in Appendix 5. Do you find that chlorine has atomic
mass 35.453? Why is the atomic mass of chlorine a fractional
number instead of a whole number, such as 35 or 36?
Recall that Dalton believed that all atoms of the same ele-
ment are identical. This turns out not to be true. Although all
atoms of the same element have the same number of protons,
there can be varying numbers of neutrons. All chlorine atoms
have 17 protons. However, some chlorine atoms have 18 neu-
trons, while others have 20 neutrons. Different forms of the
same element are called isotopes. Isotopes share the same num-
ber of protons, but have a different number of neutrons. Since
neutrons have mass, but no charge, the number of neutrons
affects the mass of an atom, but has no effect at all on its chem-
ical properties.
The atomic mass of 35.453 is the average mass of a chlorine
atom. It is equal to the weighted average of the masses of its iso-
topes. Suppose, for example, that the form of chlorine with 18
neutrons has a mass of 35 amu, while the form with 20 neutrons
has a mass of 37 amu. If 75.4% of the chlorine atoms have a mass
of 35 amu, and the rest of the atoms have a mass of 37 amu, we
can calculate the mass of an average chlorine atom.

Finding the atomic mass from the % of each isotope Follow


these steps to determine the average atomic mass of an atom
from the percent of each isotope in the element:
1. Multiply the mass of each isotope by its decimal percent.
2. Add all of the results from step 1.
If the 75.4% of the chlorine has a mass of 35 amu, then 24.6%
has a mass of 37 amu. Calculation reveals that 75.4% of 35
is 26.39 and 24.6% of 37 is 9.10. Adding the two results,

The General Structure of an Atom | 73


26.39  9.10  35.49, which is approximately equal to the listed
atomic mass of chlorine.
The atomic mass of each naturally occurring element, as
listed in reference tables, actually represents the weighted average
mass of the atoms of the isotopes of that element.

Mass Number
Isotopes of an element are chemically identical to each other.
The different number of neutrons produces a different mass in
each isotope. To distinguish one isotope from another, chemists
use the mass number of the isotope. Mass number is defined as
the sum of the number of protons and the number of neutrons.
One isotope of carbon is carbon-12. The 12 is the mass number of
this isotope. Since a carbon atom always has 6 protons (its atomic
number is six), carbon-12 must also have 6 neutrons.
mass number  p  n
where p is the number of protons, and n is the number of neu-
trons. You will recall that protons and neutrons are both called
nucleons because they are found in the nucleus. The mass number,
then, is equal to the number of nucleons.
When an element is represented with a symbol, the mass
number is usually written as a superscript before the symbol.
Carbon-12, for example, would be written 12C. The atomic
number is usually written as a subscript before the symbol. Since
carbon has 6 protons, the symbol for carbon-12 could be written
12 35
6C. The more common isotope of chlorine would be 17Cl. You
can determine the number of neutrons in 3517Cl by subtracting the
atomic number, 17, from the mass number, 35. There are 18 neu-
trons in an atom of 3517Cl. The number of neutrons in an isotope
always equals the mass number minus the atomic number.

PRACTICE
2.5 The element magnesium consists primarily of three
isotopes: 24Mg, 25Mg, and 26Mg. The composition of natu-
rally occurring magnesium is 79% 24Mg, 10% 25Mg, and

74 | Chapter 2: Atomic Structure


11% 26Mg. Find the atomic mass of Mg. (Assume that the
mass of each isotope is equal to its mass number)
2.6 For each of the following atoms, indicate the number of
protons, neutrons, electrons, and nucleons:
(a) 39
19K (b) 146C (c) 40
18Ar

Atomic Mass Versus Atomic Weight


As you know, mass and weight are different. Mass is an
unchanging property of an object. Weight depends on the gravi-
tational attraction exerted on an object in any given environ-
ment. In other words, weight changes with the location of an
object. An object will weigh slightly more in a valley than it will
on a mountaintop.
Historically, chemists sometimes used the term weight when
they should have used mass. As a result, many terms used in
chemistry still include weight. This can be very confusing, espe-
cially to beginning chemistry students. Since chemistry deals
with changes in matter and since mass represents the quantity of
matter, in this book mass will be used instead of weight. Also, mass
terms instead of weight terms will be used whenever possible.

Gram-Atomic Mass
The gram-atomic mass of an element is the atomic mass of
the element expressed in grams. Thus the gram-atomic mass of
sodium is 23.0 grams.
The number of atoms in the gram-atomic mass of each of the
elements is the same. By experiments, it can be shown that this
number is 6.02  1023. You will recognize this number as
Avogadro’s number.
The mass of a single atom can be computed from its gram-
atomic mass and the number of atoms in a gram-atomic mass. For
example, 6.02  1023 atoms of sodium have a mass of 23.0 grams.
The mass in grams of one sodium atom is
23.0 grams
 3.82  1023 gram/atom
6.02 3 1023atoms
Hydrogen has an atomic mass of 1.008 atomic mass units
(amu), or a gram-atomic mass of 1.008 grams. What is the mass of

The General Structure of an Atom | 75


a hydrogen atom? Since 1.008 grams of hydrogen contain 6.02 
1023 atoms, one hydrogen atom has a mass of
1.008 grams
 1.67  1024 gram/atom
6.02 3 1023atoms
This means that 1.008 amu, or approximately 1 amu, has a mass
of 1.67  1024 gram.

Electrons in Atoms
So far, you have a picture of the atom as a tiny nucleus with pro-
tons and neutrons and a vast surrounding space where the elec-
trons are located. Let us now concentrate on the electrons and
their arrangement in the “empty space” of the atom. This study
will lead to the modern concept of the atom.
The current model of atoms, including the arrangement of
electrons, was developed between 1900 and 1930. Many models,
based on the work of Niels Bohr, Erwin Schrödinger, and many
others, led to the modern model. The story of how scientists
arrived at today’s concept of the atom is a good example of the
way models are modified when new evidence does not agree with
the accepted model.

Emission Spectroscopy
Much of what we know about the atom and its electrons was
learned in the early 1900s from studies of the energy given off by
excited atoms. The atoms of elements are normally in a ground
state, the lowest energy state. However, when gaseous elements
are heated or subjected to an electrical discharge, the electrons in
the gaseous atoms absorb energy. The atoms are then said to be in
an excited state. Excited atoms give off energy in the form of
electromagnetic radiation.
Electromagnetic radiation is energy that travels through
space as waves at a speed of 3  108 meters per second (m/s). The
waves can be pictured as pulses that vibrate in a regularly repeat-
ing pattern (see Figure 2-5).
Waves are characterized by wavelength () and frequency (ƒ).
Wavelength is the distance between peaks or between troughs in

76 | Chapter 2: Atomic Structure


Wavelength
λ

Pulse Pulse
1 second

Figure 2-5 An electromagnetic wave

the wave. Frequency is the number of complete pulses, or cycles,


that pass a given point in one second. (In Figure 2-5, two pulses
are marked off. If they occur in 1 second, the frequency is 2 vibra-
tions per second.) Wavelength and frequency vary inversely; the
greater the frequency of a wave, the shorter its wavelength.
Electromagnetic radiation covers a broad range, or spectrum,
and includes waves from 10 kilometers in length to those with
wavelengths that are a millionth of a millionth of a meter long.
As the table below shows, ultraviolet radiation, visible light,
infrared radiation (heat), and radio waves are included in the elec-
tromagnetic spectrum. The study of electromagnetic radiation is
called spectroscopy. Emission spectroscopy is the study of the
energy—the electromagnetic radiation—emitted by excited
atoms.
The amount of energy emitted by excited atoms is related to
the frequency of the waves. This relationship of frequency to
amount of energy was established as a result of the work of Max
Planck, a German physicist. It is expressed by the formula E  hf,

Electromagnetic Radiation
3

Radio (including radar and television)


3
a333333333

a333333333

Infrared (heat)
Decreasing wavelength

Increasing frequency

Red
Orange
Yellow
u Visible light
Green
Blue
Violet
Ultraviolet
X rays
Gamma
Cosmic

Electrons in Atoms | 77
where E is energy, h is a number called Planck’s constant, and ƒ is
frequency. From the formula, you know that as ƒ increases, E also
increases. Thus the higher the frequency of the waves, the greater
is the energy given off.
Sunlight, as you probably know, is made up of light with dif-
ferent wavelengths. In the visible spectrum, red light has the
longest wavelength and the lowest frequency, violet the shortest
wavelength and the highest frequency. The different wavelengths
are separated when sunlight passes through a prism, because each
different wavelength is bent through a different angle. If the sepa-
rated wavelengths fall onto a white surface, a rainbow—a spec-
trum of colors from red to violet—is seen. The colors are not sepa-
rated from one another but blend together. This is called a
continuous spectrum (see Figure 2-6). The continuous spectrum
contains every wavelength and every frequency of light waves,
from red to violet. Since the energy can be found from the fre-
quency, the spectrum must also contain every possible amount of
energy, from the high-energy violet waves, down to the lower
energy red waves.
When the radiation from an excited atom is directed
through a prism, this radiation, too, is separated into its various
wavelengths. If the separated wavelengths are allowed to fall on
a white screen, each wavelength in the visible spectrum leaves a
colored line on the screen. (Wavelengths in the invisible part of
the spectrum can be detected by using a photographic plate
instead of a screen.) Figure 2-7 shows the spectrum formed by an

Continuous
spectrum

Red

Violet
Bulb Slit Prism

Figure 2-6 Continuous spectrum

78 | Chapter 2: Atomic Structure


Line
spectrum

Flame Slit Prism

Figure 2-7 Line spectrum

element that emits radiation of two different wavelengths in


the visible spectrum. A spectrum such as this one is called a line
spectrum. A line spectrum is discontinuous—the lines appear at
some locations but not at others. Each line represents a particu-
lar frequency of light, which means it also indicates a particular
energy of light. Excited atoms must emit light of only certain
energies. We say that the energy produced by the excited atom
is quantized. It can have only certain values within a given
range.
The spectroscopic studies of the early 1900s showed that each
element has a different line spectrum. Thus, for a given element,
a specific number of lines can be observed at specific positions on
either a screen or a photographic plate. In effect, each element
has its own spectroscopic “fingerprint.” These observations led to
a new concept of the atom—the Bohr model.

PRACTICE
2.7 Which color of visible light contains the smallest amount
of energy?
2.8 A student, in explaining the difference between “continu-
ous” and “quantized” says: “A piano is quantized, while a
violin is continuous.” Do you think this is a good analogy?
Explain your answer.

Electrons in Atoms | 79
The Bohr Model
From the results of spectroscopic studies of the hydrogen atom,
Niels Bohr, a Danish physicist, proposed a new model of the atom
in 1913. The main points of Bohr’s model are as follows:
1. Electrons revolve around the nucleus of the atom in specific
orbits, or energy levels.
2. An atom has several orbits, each representing a specific
energy level. The energy levels of an atom are very much like
the steps of a ladder. Only specific energy values (steps) can
exist—there are none between. Electrons cannot exist at any
position except one of the energy levels. The energy levels are
represented by 1, 2, 3, 4, . . . , or by E1, E2, . . . , En, or by K, L,
M, N, . . . . (The subscript n is the symbol for any whole
number.)
3. When a hydrogen atom is not excited—that is, the atom is in
its ground state—its electrons are in orbits close to the nucleus.
The electrons are at the lowest energy level, E1.
4. If a hydrogen atom receives energy—that is, if the atom is
excited—an electron is displaced farther away from the
nucleus to one of the higher energy levels, E2, E3, E4, . . . , En.
5. An atom emits energy when an electron falls from a higher
energy level to a lower energy level in one sudden drop, or
transition. The energy released is electromagnetic radiation.
6. The frequency ( ƒ) of the radiation emitted depends on the
difference between the higher and lower energy levels
involved in the transition.
Ehigher  Elower  hƒ
The Bohr model explained the discontinuous line spectra
(plural of spectrum) that had been observed in spectroscopic stud-
ies of excited hydrogen atoms. Let’s see how.
When an electron is close to the nucleus of the atom, its
potential energy is low. When the electron is farther away from
the nucleus, its potential energy is comparatively high. Now
recall that an increase in potential energy is always accompanied
by absorption of energy. Conversely, a decrease in potential
energy is always accompanied by release of energy. Thus an

80 | Chapter 2: Atomic Structure


electron of an excited atom absorbs energy in the form of heat or
electricity when it moves to a higher energy level. When the elec-
tron returns to the ground state, it emits energy. Each wave of the
emitted radiation has a specific hƒ value. This is because the tran-
sition of the electron can occur only between certain energy lev-
els. (Remember the steps of a ladder.) Hence the energy given off
is quantized.
A diagram of the Bohr model for the simplest of all elements,
hydrogen, is shown in Figure 2-8. The diagram shows six of the
possible energy levels the atom may have.
The hydrogen atom has only one electron. Ordinarily, the
electron is at the lowest possible potential energy, in energy level
E1. If energy is absorbed, the electron may be pushed away from
the nucleus to a higher energy level, E2 or E3, for example. The
potential energy of the electron will then be higher. When the
electron returns to the lower level, E1, its potential energy relative
to the nucleus decreases and energy is emitted.
As the diagram shows, some changes, or transitions, between
energy levels result in emission of energy in the visible region of
the electromagnetic spectrum. These emissions appear as lines of
different colors. Other transitions result in release of energy out-
side the visible region, such as in the ultraviolet region. You can-
not see these radiations, but you can bend them in a prism and
observe them as black lines on special photographic plates.

E6
E5
E4
E3
E2
Violet
E1

Visible
series

Blue
Red

Figure 2-8 Bohr model of the hydrogen atom

The Bohr Model | 81


In summary, the importance of the Bohr model lay in the fact
that it interpreted experimental evidence—discontinuous line
spectra—in terms of energy levels for electrons. According to the
model, electrons may exist at some energy levels but not at
others. In other words, some transitions in the potential energy of
electrons are possible, but others are not.

The Quantum Mechanical Model


The Bohr model of the atom successfully explained the lines in
the hydrogen spectrum. But when scientists tried to extend the
model to explain atoms with more than one electron, they failed.
In addition, Bohr’s model made some assumptions that were not
borne out experimentally. For example, Bohr assumed that the
orbiting electron does not approach the nucleus. Clearly, a new or
revised model was needed.
The revised model is called the quantum mechanical, or wave
mechanical, model. The words quantum and quantized are used for
variables, such as the energy of an electron, that may have certain
values only.
The two main features of the quantum mechanical model
(and differences from the Bohr model) are as follows:
1. The electron is treated mathematically as a wave in the quan-
tum mechanical model. In the Bohr model, the electron is
treated as a particle. In fact, the electron has properties of
both particles and waves.
The French physicist Louis de Broglie predicted the existence of
matter waves in 1924. Today we speak of the “duality of matter.”
Matter has some wave characteristics, just as waves have some mat-
ter characteristics. The smaller the particle being studied, the more
important the wave characteristic. If you are studying the move-
ment of a baseball, you can predict its path very accurately by just
treating the ball as matter. If you are studying the movement of an
electron, however, you must consider the behavior of waves.
2. In the Bohr model, the energy of the electron is described in
terms of a definite orbit, or pathway. In the quantum mechan-
ical model, the energy is described in terms of the probability

82 | Chapter 2: Atomic Structure


of locating the electron in a region of space outside the nucle-
us. The electron can be very close to the nucleus or very far
away. However, the probability of the electron being a certain
distance from the nucleus most of the time is high.
In 1927, Werner Heisenberg, who had studied under Niels
Bohr, proposed what came to be known as the Heisenberg
uncertainty principle. He stated that it is impossible to measure
exactly both the position and the momentum of an object simul-
taneously, and proposed an equation that computes the mini-
mum amount of error in such measurements. The error is
extremely small, but it becomes significant when applied to
objects as small as electrons. We cannot say exactly where an elec-
tron will be, but we can determine where it is most likely to be.
You can see this by studying Figure 2-9. It shows the probabil-
ity of finding the hydrogen electron (called a 1s electron) at dif-
ferent distances from the nucleus. The dark region of the cloud is
the region in space where the probability of finding the electron
is greatest. The radius (r) encloses a region within which the elec-
tron can be found about 90 percent of the time. At some large dis-
tance from the nucleus, the probability of finding the electron
approaches zero. At this distance, the electron has become com-
pletely separated from the nucleus. This region is represented by
the outer edge of the diagram in Figure 2-9.
In the quantum mechanical model the word orbital is used
to describe the shape of the region where an electron may be.
For s electrons, the region is spherical, as shown in Figure 2-9.

Quantum Numbers
The mathematics of the quantum mechanical model makes it
possible to describe the energy level of an electron using four

Figure 2-9 Electron density distribution of a hydrogen electron.

The Quantum Mechanical Model | 83


quantum numbers. The first number is the principal quantum
number, or principal energy level, n; the second quantum number,
or sublevel, l; the third quantum number, or orbital, m; and a
number describing a characteristic called electron spin. In this study,
you will be concerned chiefly with the principal quantum number.
No two electrons in an atom can have an identical set of four
quantum numbers. This is in accordance with the exclusion prin-
ciple, developed in 1925 by the Austrian-American physicist
Wolfgang Pauli. The Pauli exclusion principle states that no
more than two electrons can occupy the same orbital in an atom.
It also states that the two electrons must have opposite spins.
Let us now consider each of the quantum numbers separately.

The principal quantum number The principal quantum num-


ber, n, describes the most probable distance of the electron from
the nucleus and has whole number values—1, 2, 3, 4, . . . . These
energy levels are, in a way, similar to the K, L, M, N shells of the
Bohr model and are called the principal energy levels.
The maximum number of electrons in any principal energy
level n is 2n2. Thus in the first energy level, there can be a maxi-
mum of 2 electrons; in the second, 8; in the third, 18; and so on.
If we know the electron capacities of the principal energy
levels, and we assume that the lower energy level fills first, we
can easily predict the electron distributions for the first 18 ele-
ments. (To go beyond 18, as we shall see, additional information
is needed.)

SAMPLE PROBLEM
PROBLEM
Draw the structure of the atom with the symbol 31 15P. Show
the contents of the nucleus, and the electrons in their energy
levels.

SOLUTION
The atomic number 15 indicates that a neutral atom of phos-
phorus has 15 protons and 15 electrons. The number of neu-
trons is found by subtracting the atomic number from the
mass number (see page 74), so there are 16 neutrons.

84 | Chapter 2: Atomic Structure


The 15 electrons must be distributed as follows: The first
energy level can hold 2 electrons. The second can hold 8.
That leaves 5 electrons in the third energy level, which is
only partially filled. We might draw the structure as follows:

15p 2e– 8e– 5e–


16n

2
Energy levels
3

PRACTICE
2.9 Draw structures for the following atoms, showing the
protons and neutrons in the nucleus, and the electrons
in the energy levels:
27 35 40
(a) 13 Al (b) 17 Cl (c) 18 Ar
2.10 How many electrons would there be in the second
principal energy level of a silicon atom?

Sublevel As scientists continued to study the spectra of atoms,


they found that many of the single lines of the spectra were
actually made up of fine, closely spaced lines. The origin of all
these lines could not be explained by transitions, or jumps, of
electrons between the principal energy levels. This led to the
view that the principal energy levels are divided into sublevels.
The energy values of the sublevels differ by only small amounts.
Sublevels are described by the second quantum number, l.
The number of sublevels in any principal energy level is equal
to the principal quantum number, n. Thus, when n  1, the

The Quantum Mechanical Model | 85


first principal energy level has one sublevel: the s sublevel. The
two electrons that may be in the first principal energy level are
called 1s electrons.
The second principal energy level (n  2) has two sublevels.
The first sublevel is again called the s sublevel. The second sublev-
el is called the p sublevel. The electrons in the first sublevel are 2s
electrons. The electrons in the second sublevel are 2p electrons.
There may be two 2s electrons in the first sublevel. There may be
up to six 2p electrons in the second sublevel. Thus the second
principal energy level can have a maximum of 8 electrons.
The third principal energy level (n  3) is split into three sub-
levels: 3s, 3p, and 3d. There may be a total of 18 electrons. The
fourth principal energy level (n  4) follows the pattern that
has been developing. There are four sublevels in the fourth princi-
pal energy level: 4s, 4p, 4d, and 4ƒ. There may be a total of 32
electrons.
The arrangement of electrons in principal energy levels and
sublevels is shown in the table below.

Maximum Number
Principal of Electrons
Quantum in Each Sublevel Total
Principal Number Number
Energy Level (n) s p d f of Electrons

1 1 2 2
2 2 2 6 8
3 3 2 6 10 18
4 4 2 6 10 14 32

Orbital Careful analysis of the lines of spectra show that sub-


levels are made up of orbitals. An orbital is a region of space
around a nucleus in which the probability of finding an electron
is high. Orbitals represent the third quantum number, m. Each
sublevel has a specific number of orbitals. There is one orbital in
an s sublevel, three orbitals in a p sublevel, five orbitals in a d sub-
level, and seven orbitals in an ƒ sublevel.
Each sublevel and its orbitals are related to the shape of the
region that an electron may occupy. Any s sublevel is spherical, as
shown in Figure 2-9 on page 83. Sublevels described as p are
shaped like a dumbbell, as shown in Figure 2-10. The three
orbitals in a p sublevel are oriented along three axes: x, y, and z.

86 | Chapter 2: Atomic Structure


y py y

px x x

z z
pz

Figure 2-10 The shape of orbitals in a p sublevel

The shapes of d and ƒ sublevels are difficult to represent with a


simple drawing and need not concern you.
It is important to realize that an orbital does not represent the
path of an electron; it represents a region in which the electron
can be found 90% of the time. To illustrate this concept, suppose
that while in the field, the New York Yankees’ shortstop, Derek
Jeter, wore shoes that made a mark wherever he went. At the end
of a few innings, as shown in Figure 2-11 on page 88, there would
be marks all over the left side of the infield, and part of the out-
field, but there would clearly be a region where Mr. Jeter could be
found the vast majority of the time. This region would be Derek
Jeter’s orbital, but we prefer to call it “shortstop.”*

Electron spin Spin is the fourth quantum number. An electron


acts as if it were spinning on an axis. When a negatively charged
object spins, it creates a magnetic field. If it spins counter clock-
wise, the north pole of the magnetic field is “up” while if it spins
clockwise, the north pole is “down.” For this reason, the spin is
generally represented in terms of the resulting magnetic field—
either up or down.
A maximum of two electrons can occupy one orbital. The two
electrons can have the same first three quantum numbers, but in
accordance with the Pauli exclusion principle, the fourth quan-
tum number must be different. Thus the two electrons in an
orbital must have opposite spins.
Within a given sublevel in a free atom, the energies of orbitals
are equal.
*The author wishes to make it clear that he is NOT a Yankees fan.

The Quantum Mechanical Model | 87


Jeter’s
“orbital”

Figure 2-11 A baseball player’s “orbital”

Orbitals and their electrons can be shown in various ways. In


this book, an orbital will be represented as . An orbital with
one electron will be represented as or , depending on the
spin of the electron. An orbital with two electrons will be repre-
sented as . Some examples are shown in the following chart.

1s 1s 1s 2p

One electron One electron with Two electrons Three orbitals


in 1s orbital opposite spin with opposite in 2p sublevel.
in 1s orbital spins in filled A total of six
1s orbital electrons can
be contained
in this sublevel,
but only one is
present here.

88 | Chapter 2: Atomic Structure


Quantum Numbers—A Summary
Some of the information derived from quantum numbers is
summarized in the following table. You will find it useful to refer
to this table as you go on with your study.

Principal Number of Total


Energy Orbitals Number of
Level Sublevels (m) per Electrons
(n) (l) Sublevel per Sublevel

1 s (spherical) 1 2

2 s 1 2 8
r
p (dumbbell) 3 6

3 s 1 2
p 3 6 s 18
d 5 10

4 s 1 2
p 3 6
t
d 5 10 32
f 7 14

Electron Configurations
Electrons normally occupy the lowest energy orbital available.
Figure 2-12 on page 90, shows the order in which the orbitals are
filled. Beginning at the bottom of the diagram, the 1s orbital is at
the lowest energy level. It can receive two electrons. When this
orbital is filled, an electron goes to the orbital with the next low-
est energy level, 2s. This energy level also can receive two elec-
trons. When this orbital is filled, the orbital with the next higher
energy level will be occupied. The p orbitals have the next higher
energy values. A total of six electrons can be added to complete
this energy level.
Generally, the orbitals increase in energy value in the order s,
p, d, and ƒ. Notice, however, that the 4s orbital is at a slightly
lower energy level than the 3d orbitals. Also, the 5s orbital is
lower than the 4d orbitals. In other words, the s orbital of a

Electron Configurations | 89
s p d f
6p
5d
4f
6s

5p
4d
5s

4p
3d
Relative energies of orbitals

4s
Increasing energy

3p
3s

2p
2s

1s

Figure 2-12 Order of filling orbits

higher principal energy level may be occupied before the d


orbitals of a lower principal energy level.

Hund’s Rule
A p sublevel can hold up to six electrons—two in each of the
three p orbitals . Suppose that a particular p sublevel has
only two electrons in it. How are they arranged? Here are four
possibilities:

1 2 3 4
In structure 1, both electrons are in the same orbital. Electrons
in the same orbital are called paired electrons. In structures 2, 3,

90 | Chapter 2: Atomic Structure


and 4, the electrons are in separate orbitals. A single electron in
an orbital is called an unpaired electron.
Hund’s rule predicts the way electrons will fill the orbitals
within a given sublevel. It states that:
1. No orbital in a sublevel may contain two electrons unless all
of the orbitals in that sublevel contain at least one electron.
In other words, the orbitals fill one electron at a time.
2. All unpaired electrons on a given atom have the same spin.
We can see that structure 1 is incorrect, because it has two
electrons in the same orbital while other orbitals in the sublevel
are empty. Structure 2 is also incorrect, because the unpaired
electrons do not have the same spin. Structures 3 and 4
are both correct. However, it is customary to fill the orbitals
from left to right when illustrating the electron configuration
of an atom. Therefore, structure 3 is the one that would
normally be used to illustrate a p sublevel containing two
electrons.

Electron Configuration of the Elements


Let us now fill in electrons at the proper energy levels for
the first 21 elements. We will take the elements in order of
increasing atomic number and make sure that each successive
electron enters the lowest energy level available. As you work
with this section, it will be helpful for you to refer to the
Periodic Table in Appendix 5. You will notice that the elements
are arranged in the table in order of atomic number. Also, the
elements are placed in certain horizontal rows, also called peri-
ods, and in vertical columns, also called groups or families. The
periods are numbered from 1 to 7, and the groups from 1 to 18.
(Older versions of the table used Roman numerals to number
the groups, sometimes followed by a letter A or B.) You will
understand the significance of the periods and groups as you go
on. The Periodic Table will also be discussed at length in
Chapter 5.

The first principal energy level In hydrogen, the single electron


enters the first principal energy level (n  1), which has only an s

Electron Configurations | 91
sublevel. The s sublevel contains one orbital. The electron config-
uration of hydrogen can be shown this way:
1s
H (1)
Helium, atomic number 2, has two electrons in the 1s sublev-
el. These electrons fill the 1s orbital. The electron configuration is
shown as
1s
He (2)
Because two electrons are the maximum number that can
occupy any orbital, helium has a completely filled 1s orbital. In
addition, two electrons are the maximum number that can occu-
py the first principal energy level. Helium has therefore also com-
pleted the first principal energy level.
The horizontal arrangement of hydrogen and helium make up
the first row, or period, of the Periodic Table.

The second principal energy level Lithium, atomic number 3,


first fills the sublevel of lowest energy, the 1s sublevel, with two
electrons. The third electron enters the next lowest energy level
available—the 2s sublevel of the second principal energy level
(n  2). This energy level has two sublevels, s and p. Beryllium,
atomic number 4, completes the 2s sublevel. In boron, atomic
number 5, the fifth electron enters the p sublevel, which contains
three p orbitals. The electron configurations of lithium, berylli-
um, and boron can be shown as

1s 2s 2p
Li (2-1)
Be (2-2)
B (2-3)
In carbon, atomic number 6, the sixth electron enters the sec-
ond p orbital instead of the first p orbital, as predicted by Hund’s
rule. This is due to the tendency of particles with similar charges
to repel one another and thus to move as far apart as possible.
1s 2s 2p
C (2-4)

92 | Chapter 2: Atomic Structure


In the same manner, electrons are added to nitrogen, oxygen,
fluorine, and neon until the second principal energy level is com-
plete. The electron configurations are given below.
1s 2s 2p
N (2-5)
O (2-6)
F (2-7)
Ne (2-8)
Neon fills the second principal energy level. The second row
of the Periodic Table contains eight elements.

The third principal energy level The eleventh electron in sodi-


um must enter the third principal energy level in the 3s sublevel.
1s 2s 2p 3s 3p
Na (2-8-1)
The electron configurations of the next seven elements can be
completed in the same way that the configurations for the ele-
ments in the previous principal energy level are completed.

1s 2s 2p 3s 3p
Mg (2-8-2)
Al (2-8-3)
Si (2-8-4)
P (2-8-5)
S (2-8-6)
Cl (2-8-7)
Ar (2-8-8)
If you compare the electron structures of the elements in the
vertical columns of the Periodic Table, you will see the beginning
of similarities. In lithium and sodium, for example, the s sublevel
is half-filled. Lithium and sodium are the first two elements of
Group 1—the alkali metal family. Other common members of
this family include potassium, rubidium, and cesium. The pres-
ence of the half-filled s sublevel accounts for similar properties in
this group of elements. (Hydrogen also has a half-filled s sublevel.
However, for reasons that will be discussed later, hydrogen does
not belong to the alkali metal family.)

Electron Configurations | 93
Transition elements The maximum number of electrons in the
third principal energy level is 18. This level contains a d sublevel
with five d orbitals that have a total of ten electrons. When these
ten electrons are added to the eight electrons in the 3s and 3p
orbitals, the maximum number of 18 electrons (n  3) is reached.
The nineteenth electron of potassium might be expected to
enter the 3d sublevel. However, if you check Figure 2-12 on page 90,
you will notice that the 4s orbital is lower in energy than the 3d
orbital. The nineteenth electron of potassium therefore enters the
4s orbital. The twentieth electron of calcium completes this orbital.

1s 2s 2p 3s 3p 4s
K (2-8-8-1)
Ca (2-8-8-2)

The next most energetic sublevel is 3d. The twenty-first elec-


tron of scandium enters the 3d sublevel. In terms of principal
energy levels only, we can say that the electron configuration of
scandium is 2-8-9-2.

1s 2s 2p 3s 3p 4s 3d
Sc

The next nine elements (titanium through zinc) complete this


sublevel, which is in the third principal energy level. When this
sublevel is complete, electrons enter the 4p sublevel. Elements
that complete inner, or lower, energy levels before completing
outer, or higher, energy levels are called transition elements.
Transition elements are discussed again in Chapter 5.
The third row of the Periodic Table has eight elements.
However, the third principal energy level has 18 elements. Ten of
these elements (scandium through zinc) are transition elements.
They are in the fourth row of the Periodic Table.
The Periodic Table in Appendix 5 gives the electron configura-
tions of most of the elements in terms of their principal energy
levels.
As you learned from Bohr theory, electrons may absorb energy
and jump to higher energy levels. These higher energy levels are
called excited states. When an element is in an excited state, it
will not have the electron structure shown in this Periodic Table.

94 | Chapter 2: Atomic Structure


The structures in the Periodic Table are all for elements in their
ground states.

Using the reference table to fill the orbitals Our Periodic Table
shows the electron configurations only in terms of the shells, or
principal energy levels. From this information it is easy to also
determine the orbital configurations. We need to remember that
the electron capacities of the s, p, d and f sublevels are 2, 6, 10
and 14, respectively. For example, consider the electron configu-
ration of a Ca atom. Our table gives us the configuration “2-8-8-
2”. There are 2 electrons in the first shell, 8 in the second, 8 in
the third, and 2 in the fourth. When a shell contains only 2
electrons, only the s sublevel can be involved. A shell with 8
electrons must contain 2 electrons in the s sublevel, and 6 elec-
trons in the p. Filling in the orbitals gives us the structure shown
on page 94. Now examine the configuration of an iron atom,
element number 26. The Periodic Table lists the configuration as
“2-8-14-2.” What orbitals are used by the 14 electrons in the
third shell? The s holds 2 electrons, and the p 6, which leaves 6
electrons in the 5 orbitals of the d sublevel. The correct configu-
ration of a ground state iron atom shows that it contains 4
unpaired electrons.

1s 2s 2p 3s 3p 4s 3d

PRACTICE
2.11 Using arrows to represent electrons, as shown in this chap-
ter, draw the orbital configurations of the following atoms
in the ground state:
(a) N (b) Si (c) Mn (d) Zn
2.12 How many unpaired electrons are there in each of the fol-
lowing elements, in the ground state?
(a) 8O (b) 15P (c) 18Ar (d) 24Cr
2.13 Each of the four elements on page 96 is shown with an
incorrect electron configuration. In each case, indicate why

Electron Configurations | 95
the configuration is incorrect, and draw the correct config-
uration.
1s 2s 2p
(a) 6C

1s 2s 2p
(b) 9F

1s 2s 2p 3s
(c) 12Mg

1s 2s 2p
(d) 7N

The Notation System of Showing Electron Configuration


You have been working with a pictorial way of showing the
number of electrons in an atom and the distribution of the elec-
trons in orbitals. By this method, the one electron in hydrogen
can be shown as

1s
H
and the eight electrons in oxygen can be shown as

1s 2s 2p
O
Electron configuration can also be shown by a notation sys-
tem. By this method, the hydrogen electron is represented by 1s1.
The electrons in oxygen are represented by 1s22s22p4. In both
cases, the coefficients refer to the principal energy level (the first
quantum number).
The exponents, or superscripts, indicate the number of elec-
trons at the specified sublevels.
The order of notation is important. Refer again to the ele-
ments of the fourth row. Potassium has one electron in the fourth
principal energy level and none in the 3d sublevel. Calcium
has two electrons in the fourth principal energy level and none in

96 | Chapter 2: Atomic Structure


the 3d sublevel. The electron configuration of potassium is
1s22s22p63s23p64s1. Calcium is 1s22s22p63s23p64s2.
Beginning with scandium, electrons are added to the 3d sublevel.
1s 2s 2p 3s 3p 3d 4s
Sc
The electron configuration of scandium would be written
1s22s22p63s23p63d14s2. Notice that the 3d sublevel is written
before the 4s, even though the 4s filled first. (See the configura-
tion of calcium, above.) It is customary when writing electron
configurations to keep the sublevels in the same principal energy
level together. Doing so makes it easier to view the contents of
each principal energy level. In scandium, you can see that the
first principal energy level has 2 electrons, the second has 8, the
third has 9 and the fourth has 2.
A shortcut method of notation is sometimes used. Iron, one of
the transition elements, has the electron configuration 1s22s2
2p63s23p63d64s2. The electron configuration of iron can also be
shown as [Ar]3d64s2. [Ar] represents the electron configuration of
the element argon: 1s22s22p63s23p6. When [Ar] is used to stand
for the configuration of the first eighteen electrons of iron, only
the eight electrons at the outer energy levels of the iron atom
need be shown.
Argon is one of the so-called noble gases. The outermost prin-
cipal energy levels of the noble gases have their full complement
of electrons. This means that electrons from other atoms cannot
enter these levels. As a result, the noble gases do not readily form
chemical bonds with other elements. The other noble gases are
helium, neon, krypton, xenon, and radon. The noble gases form
Group 18 of the Periodic Table. (They were also called inert gases
because of their limited chemical activity.)
With their filled energy levels, all the noble gases can be used
as shortcuts for writing electron notations. Thus magnesium can
be shown as [Ne]3s2 and potassium as [Ar]4s1.

Valence Electrons
The electrons in the outer energy levels of atoms are those that
are involved in the formation of chemical bonds. As you will later

Valence Electrons | 97
learn, in Chapter 3, atoms may be bonded by losing, gaining, or
sharing electrons.
The electrons of an atom that are likely to become involved in
the formation of bonds are called the valence electrons. In all
the elements of Groups 1, 2, 13–18, that is, in all elements except
the transition elements, Groups 3–12, the valence electrons are all
the electrons in the outermost principal energy level that con-
tains electrons. Take, for example, an element with the electron
configuration 1s22s22p63s23p2. This element contains four
valence electrons, because there are four electrons in the third
principal energy level. For elements in Groups 1, 2, 13–18, the
number of valence electrons is also the same as the number in the
units place of the group number of the element. Thus the ele-
ments in Group 1 have the valence electron, and those in Group
15, have five valence electrons.
Estimating the number of valence electrons for the transition
elements is more difficult and does not need to be studied in this
course. It is worth noting, however, that a transition element may
have valence electrons in more than one principal energy level.
For example, the electron configuration of an iron atom is
[Ar]3d64s2. When iron forms one type of bond, three electrons are
involved: two 4s electrons and one 3d electron.

SAMPLE PROBLEM
PROBLEM
The electron configuration for a phosphorus (P) atom is
1s22s22p63s23p3. Indicate for this atom the number of
(a) completely filled principal energy levels
(b) completely filled sublevels
(c) completely filled orbitals
(d) unpaired electrons

SOLUTION
(a) The first and second principal energy levels are filled,
with two and eight electrons respectively. The third
principal energy level has five electrons in it. It is not
completely filled, since it can hold 18 electrons. There
are two completely filled principal energy levels.

98 | Chapter 2: Atomic Structure


(b) The 1s, 2s, 2p, and 3s are completely filled. The 3p is only
half filled. There are four completely filled sublevels.
(c) An s sublevel contains one orbital; a p sublevel con-
tains three orbitals. The total number of completely
filled orbitals is six, as shown in the diagram below.

Filled orbitals

ls2 2s2 2p6 3s2 3p3


(d) As you can see in the diagram above, there are three
unpaired electrons in a phosphorus atom.

PRACTICE
2.14 For an oxygen atom in the ground state, find the number
of (a) unpaired electrons (b) completely filled principal
energy levels (c) completely filled orbitals.
2.15 A certain atom in an excited state has the electron configu-
ration 1s22s12p3.
(a) While the atom is in this state, how many of the elec-
trons are unpaired?
(b) What is the electron configuration of this atom in the
ground state?

Ionization Energy
All atoms are electrically neutral. They have an equal number of
positively charged protons in the nucleus and negatively charged
electrons outside the nucleus. Recall, though, that one way atoms
are bonded is by the loss of one or more electrons. The loss of an
electron from a neutral atom results in the formation of a posi-
tively charged particle, called a positive ion.
Electrons are held in the atom by the attractive force of the
positively charged nucleus. Energy must therefore be expended in
removing an electron from the atom to form a positive ion. The

Ionization Energy | 99
energy required to remove the most loosely held electron from an
isolated, neutral, gaseous atom is the ionization energy.
Let us represent a neutral, gaseous atom of element X as X0.
An electron removed from X0 to form the positive ion X
involves the first ionization energy. Another electron removed
from X1 to form X2 ion involves the second ionization energy.
The removal of another electron from X2 ion to form X3 ion
involves the third ionization energy.
As successive electrons are removed, the original particle
becomes more positively charged and attracts electrons more
strongly. As a result, it becomes progressively harder to remove
electrons as the charge on the ion increases. Ionization energies
therefore increase as each additional electron is removed.
The amount of energy needed to remove the most loosely held
electron from a gaseous atom depends on the following conditions:
1. The charge of the nucleus. As the nuclear charge (atomic
number) increases, the force of attraction between the nucle-
us and the electrons increases.
2. The distance from the nucleus to the outermost energy level
that has electrons. This distance is called the radius of the
atom. As the number of occupied principal energy levels
increases, the radius of the atom increases. Because the elec-
tron is farther from the nucleus, it is held more loosely, and
less energy is required to remove it from the atom.
3. The screening, or shielding, effect of the electrons of the inner
energy levels. This effect tends to reduce the force exerted by
the nucleus on the electrons in the outer energy level.
4. The sublevel of the outer electrons. Generally, s electrons are
more tightly held to the nucleus (they are at a lower energy
level) than are p electrons.
Ionization energy is generally expressed in kilojoules per
mole. For example, it requires 520 kJ to remove one mole of elec-
trons from one mole of lithium atoms.
The following table lists the first ionization energies for a
number of elements. The elements are arranged in the order in
which they appear in the Periodic Table.
The same ionization energies are plotted on the graph shown
in Figure 2-13. The change of ionization energy as atomic num-
bers increase is repeated regularly, as you can see in the graph.

100 | Chapter 2: Atomic Structure


Ionization Ionization
Atomic Energy Atomic Energy
Number Element (kJ/mole) Number Element (kJ/mole)

1 H 1312 11 Na 496
2 He 2372 12 Mg 736
3 Li 520 13 Al 578
4 Be 900 14 Si 787
5 B 801 15 P 1012
6 C 1086 16 S 1000
7 N 1402 17 Cl 1251
8 O 1314 18 Ar 1521
9 F 1681 19 K 419
10 Ne 2081 20 Ca 590

Such a change is called periodic. Look at the elements of Period 2


(lithium, Li, to neon, Ne) and Period 3 (sodium, Na, to argon, Ar).
The ionization energies for the elements between lithium and
neon generally increase. Then there is a large drop to sodium
(and the ionization energy for sodium is lower than the ioniza-
tion energy for lithium). Between sodium and argon, the ioniza-
tion energies again generally increase. Then there is another large
drop to potassium, K (and the ionization energy for potassium is
lower than the ionization energy for sodium). The general trend
is an increase of ionization energy within a period (lithium to
neon) and a decrease within a group (lithium to potassium).
These observations agree with the conditions listed previously.
(Some irregularities in these trends can be observed. Ionization
energy decreases from beryllium, Be, to boron, B; from nitrogen,
N, to oxygen, O; from magnesium, Mg, to aluminum, Al; and

3000 He
Ionization energy (kJ/mole)

Ne
2500
F Ar
2000 N
Cl
1500 Be O P
H
C Si
1000 Mg S Ca
B
500 Li Al
Na K
0
0 2 4 6 8 10 12 14 16 18 20
Atomic number

Figure 2-13 Trends in ionization energies

Ionization Energy | 101


from phosphorus, P, to sulfur, S. The irregularities can be
explained by a more detailed study of the electron structure in
each pair of atoms.)
Ionization energy is a valuable measure of how firmly the val-
ence electrons are held in a given atom. This information, in turn,
helps to explain the formation of chemical bonds between atoms.

Electron Affinity and Electronegativity


Atoms can be bonded by losing, gaining, or sharing electrons.
When an atom loses an electron and becomes a positively
charged ion, energy is absorbed. The amount of energy needed is
the ionization energy. The opposite process may also occur. An
atom may receive an electron and become a negatively charged
ion. In this process, energy generally is released. The amount of
energy released is called electron affinity.
The ability of atoms in molecules to attract the electrons that
bond the atoms also can be compared. This ability, which the
American chemist Linus Pauling (1901–1994), has called “the
power of an atom in a molecule to attract electrons to itself,” is
called electronegativity.
Chemists have set up a scale of the relative electronegativities
of the elements. Electronegativity values of some elements are
given in Figure 2-14. Of the elements shown, fluorine, F, has the
greatest attraction for electrons. Fluorine is therefore given the
highest electronegativity value (4.0). Further study of the elec-
tronegativity values in the table shows:
1. In every horizontal row, the electronegativity value is lowest
for the elements in Group 1 (the alkali metals).
2. The electronegativity values increase in a regular manner
from the alkali metals to the elements in Group 17 (the halo-
gen elements).
3. In every vertical group of the Periodic Table (with some
minor exceptions), the electronegativity values decrease from
the top to the bottom of the group. The most electronegative
element is at the top of Group 17.
4. The least electronegative element (excluding the noble gases)
is at the bottom of Group 1.

102 | Chapter 2: Atomic Structure


ELECTRONEGATIVITIES OF SOME ELEMENTS
(on the arbitrary Pauling scale)
1

H
2.1
2 13 14 15 16 17

Li Be B C N O F
1.0 1.6 2.0 2.6 3.0 3.4 4.0

Na Mg Al Si P S Cl
0.9 1.3 1.6 1.9 2.2 2.6 3.2

K Ca Ga Ge As Se Br
0.8 1.0 1.8 2.0 2.2 2.6 3.0

Rb Sr I
o.8 1.0 2.7

Cs Ba
0.8 0.9

Figure 2-14 Partial Periodic Table showing electronegativities

5. Except for some irregularities in the values for ionization


energies, ionization energies and electronegativities follow
similar trends. If you think about it, you will see why this is
so. Atoms of elements that have low ionization energies exert
a weak attractive force on their own outer electrons and also
on the outer electrons of other atoms.
Ionization energies, electron affinities, and electronegativities
are examples of some periodic properties of the elements. These
properties are discussed fully in Chapter 5, along with other peri-
odic properties.

TAKING A CLOSER LOOK

Order of Fill
The order in which electrons go into the available sublevels is
called the order of fill. There are rules that predict the order of fill
for most elements. You can use these rules to predict an electron

Taking A Closer Look | 103


configuration for an element from its atomic number alone, with-
out consulting a reference table.
The sublevels fill in the following order: 1s, 2s, 2p, 3s, 3p, 4s,
3d, 4p, 5s, 4d, 5p, 6s, 4ƒ, 5d, 6p, 7s, 5ƒ, 6d. Instead of memorizing
the order above, you may prefer to use a chart like this one:

1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d 6f
7s 7p 7d 7f

This chart simply lists all of the sublevels in each of the seven
principal energy levels, one under another. By drawing diagonal
lines, as shown, you obtain the correct order of fill. To obtain the
electron configuration for an element, you simply fill the sub-
levels, in the order shown, until you run out of electrons.
Remember that an s sublevel can hold 2 electrons, a p can hold 6,
a d can hold 10, and an f can hold 14 electrons.

SAMPLE PROBLEM
PROBLEM
What is the probable electron configuration of an arsenic
atom (atomic number  33)?

SOLUTION
You need to fill in 33 electrons. Following the order of fill,
begin with 1s22s22p63s23p6. Thus far you have used up 18
electrons. The next sublevel to fill is the 4s, followed by the
3d. If you fill the 4s with 2 electrons, there are 10 electrons left
for the 3d and 3 electrons for the 4p, giving us the correct con-
figuration: 1s22s22p63s23p63d104s24p3 (Note that you write the
3d before the 4s, even though the 4s fills first. Recall the cus-
tom of keeping sublevels in the same principal energy level
together when you write these configurations.)

104 | Chapter 2: Atomic Structure


PRACTICE
2.16 Without using a reference table, write the electron config-
urations for elements with the following atomic numbers.
(a) 25 (b) 40 (c) 29

Exceptions to the Order of Fill


If you tried Practice 2.16, the structure you obtained for ele-
ment 29, (Cu) was probably 1s22s22p63s23p63d94s2. However, the
structure copper is 3d104s1 instead of 3d94s2. Copper is one of sev-
eral exceptions to the order of fill. Let us examine why some of
these exceptions occur.
As you move farther out from the nucleus, the energy differ-
ences between the sublevels become smaller and smaller. The 4s
and 3d, for example, are very close in energy. The 4s generally fills
before the 3d. However, there is extra stability when p, d, or ƒ sub-
levels are exactly filled and exactly half filled. By putting 10 elec-
trons into the 3d sublevel it is filled completely, giving it added
stability and making it just lower in energy than the 4s.
You can see a similar occurrence in chromium, which has the
configuration [Ar]3d54s1. Here the 3d sublevel is exactly half
filled. The extra stability causes an electron to prefer the 3d sub-
level to the 4s. There are many other exceptions to the order of
fill. Not all of them have been completely explained.

Trends in Ionization Energy


The trends in ionization energy are shown in Figure 2-13 on
page 101. You can see that as you move from left to right, across a
period, the ionization energy generally increases. In Period 2,
from lithium, Li, to neon, Ne, you see this trend clearly. However,
you can see two exceptions to the upward trend. The ionization
energy dips between beryllium Be, and boron, B, and then dips
again between nitrogen, N, and oxygen, O. Notice that similar
dips occur in every period, not just in Period 2. Why?
Beryllium has the configuration 1s22s2. the configuration of
B is 1s22s22p1. Since boron has one additional proton pulling on
its electrons, you might expect its ionization energy to be higher
than that of beryllium. However, the electron being removed

Taking A Closer Look | 105


from the boron is a 2p electron, while the electron removed
from a beryllium atom would be a 2s electron. A 2p electron is
screened by the 2s electrons, and thus, lost more easily.
The dip between nitrogen and oxygen can be explained
using a principle already mentioned, the extra stability of half-
filled sublevels. The configuration of nitrogen is 1s22s22p3. The
p sublevel is half filled. In oxygen, which is 1s22s22p4 the p is no
longer exactly half filled, and it is easier to remove an electron
from it.

Electron Configurations of Ions


Elements may gain or lose electrons to form charged parti-
cles called ions. The electron configurations of these ions are
not listed on most reference tables, because they can generally
be determined from the configurations of the atoms.
When atoms lose electrons they form positive ions. These
ions are positively charged because, having lost electrons, they
now contain more positive protons than negative electrons.
The electrons lost are from the highest principal energy level of
the atom. For example, in the transition elements, the outer s
electrons are lost before the inner d electrons. Consider the
structure of magnesium (Mg), element number 12,
1s22s22p63s2. To form a 2 ion, it must lose two electrons.
These electrons come from the last principal energy level.
Taking two electrons from the 3s sublevel leaves a configuration
for the Mg2 ion of 1s22s22p6. This configuration is identical to
that of a neutral atom of neon. Particles with the same number
of electrons are said to be isoelectronic. Thus the Mg2 ion is iso-
electronic to a neon atom.
Because of the loss of electrons, positive ions are always
smaller than their neutral atoms. In the case of the Mg2 ion,
an entire principal energy level has been lost. Because it now
has only two principal energy levels, the Mg2 ion is much
smaller than the magnesium atom (less than half as large).
The sodium ion, Na, has exactly the same electron configu-
ration as the Mg2 ion. Sodium atoms have 11 electrons, so the
1 ion has 10. Magnesium atoms have 12 electrons, so the 2
ion has 10. How would a Na ion and a Mg2 ion compare in
size? They have exactly the same number of electrons and
exactly the same electron configurations. However, magnesium

106 | Chapter 2: Atomic Structure


has 12 protons, while sodium has 11 protons. Since there is a
greater positive charge pulling on the electrons in the magne-
sium ion, it is smaller than the sodium ion. Generally speaking,
the larger the positive charge in the nucleus of an isoelectronic
ion, the smaller the ion.
Negative ions have more electrons than protons. The O2
ion, for example, has 10 electrons. Oxygen has an atomic num-
ber of 8. When oxygen becomes a 2 ion it gains two electrons.
The O2 ion, then, has the configuration 1s22s22p6. This makes
the O2 ion isoelectronic to the Na ion and the Mg2 ion dis-
cussed above. However, negative ions are larger than their neu-
tral atoms, because the additional electrons repel each other. The
O2 ion is larger than Na or Mg2 and larger than neutral Ne,
which also has 10 electrons. Generally speaking, the more nega-
tive the isoelectronic ion, the larger its radius.

PRACTICE
2.17 Titanium has an atomic number of 22. The Ti2 ion has
two unpaired electrons.
(a) How many electrons are there on this ion?
(b) What is the electron configuration of a Ti2 ion?
2.18 What is the electron configuration of an Fe3 ion? Iron is
atomic number 26. (Hint: the correct structure has five
unpaired electrons.)

CHAPTER REVIEW

The following questions will help you check your understanding


of the material presented in the chapter.
Data required for answering questions in this chapter will be
found in Table S and in the Periodic Table in Appendix 5.

Chapter Review | 107


1. Which is the correct orbital notation for the electrons in the
second principal energy level of a beryllium atom in the
ground state?
2s 2p 2s 2p

(1) (3)

2s 2p 2s 2p

(2) (4)

2. An atom with the electron configuration 1s22s22p63s23p64s2


has an incomplete (1) second principal energy level (2) 2s
sublevel (3) third principal energy level (4) 3s sublevel.
3. How many electrons are in a neutral atom of 73Li? (1) 10 (2) 7
(3) 3 (4) 2
4. When an aluminum atom loses three electrons it would form
an ion with a charge of (1) 1 (2) 1 (3) 3 (4) 3
5. Which set of particles is arranged in order of increasing mass?
(1) H2, H, H (2) H, H, H2 (3) H2, H, H (4) H, H, H2
6. Isotopes of the same element do not have the same (1) num-
ber of electrons (2) atomic number (3) mass number (4) elec-
tron configuration.
7. How many moles of helium contain the same number of
molecules as 4 moles of neon? (1) 20 (2) 10 (3) 8 (4) 4
8. Which correctly represents an atom of neon containing 11
11 20 21 21
neutrons? (1) 10Ne (2) 11Ne (3) 10Ne (4) 11Ne
9. A Mg2 ion has the same electron configuration as (1) Na0
(2) Ar0 (3) F (4) Ca2
10. An atom of which element in the ground state contains elec-
trons with a principal quantum number (n) of 4? (1) Kr (2) Ar
(3) Ne (4) He
11. Which energy level transition represents the greatest
absorption of energy? (1) 1s to 3p (2) 2p to 3s (3) 3s to 3p
(4) 3s to 4s
12. Which is the electron configuration of the element having
the highest ionization energy? (1) 2-3 (2) 2-4 (3) 2-6 (4) 2-7

108 | Chapter 2: Atomic Structure


13. Energy in the form of light is emitted when an electron in a
hydrogen atom moves from a 3s sublevel to a (1) 4s (2) 3p
(3) 3d (4) 2s
14. Which element requires the least amount of energy to
remove its most loosely bound electron? (1) Li (2) Mg (3) K
(4) Ca
1 2
15. The isotopes 1H and 1H have the same (1) atomic number
(2) mass number (3) number of neutrons (4) density.
16. What is the total charge on an ion that contains 10 electrons,
13 protons, and 15 neutrons? (1) 1 (2) 1 (3) 3 (4) 3
17. In which way does an Na ion differ from an Na0 atom?
(1) atomic number (2) mass number (3) number of electrons
(4) nuclear charge
18. What is the maximum number of electrons that can occupy
the 3d sublevel? (1) 6 (2) 8 (3) 10 (4) 14
19. An element in its ground state has 5 valence electrons.
Which is the correct distribution of these electrons?
s p s p

(1) (3)

s p s p

(2) (4)

20. What is the number of orbitals in a p sublevel? (1) 7 (2) 6


(3) 3 (4) 1
21. Which element in the ground state has a valence electron in
a p subshell? (1) Na (2) Mg (3) Al (4) Be
22. The maximum number of electrons possible in any principal
energy level (principal quantum number  n) is equal to
(1) n (2) 2n (3) n2 (4) 2n2
23. Which represents the electron configuration of an isotope of
oxygen in the ground state? (1) 1s22s22p1 (2) 1s22s22p2
(3) 1s22s22p3 (4) 1s22s22p4
24. As the elements in Period 3 are considered in order of increas-
ing atomic number, the number of principal energy levels

Chapter Review | 109


in each successive element (1) decreases (2) increases
(3) remains the same.
25. Which is the electron configuration for a neutral atom in the
ground state? (1) 1s22s23s1 (2) 1s22s22p43s1 (3) 1s2 2s22p63p1
(4) 1s22s22p63s1
26. What is the number of sublevels in the third principal energy
level? (1) 1 (2) 2 (3) 3 (4) 4
27. An ion has the electron configuration 1s22s22p63s23p6 and a
charge of 1. The number of protons in its nucleus is (1) 16
(2) 17 (3) 18 (4) 19.

Base your answers to questions 28 through 30 on the following


electron configuration of a neutral atom:
1s22s12p3
28. How many protons are in the nucleus of this atom? (1) 6
(2) 5 (3) 3 (4) 2
29. How many principal energy levels are in this electron struc-
ture? (1) 1 (2) 2 (3) 3 (4) 4
30. How many incomplete orbitals are indicated by this electron
configuration? (1) 1 (2) 2 (3) 3 (4) 4
31. When the aluminum atom is in the ground state, how many
orbitals contain only one electron? (1) 1 (2) 2 (3) 3 (4) 13
32. Which orbital contains the valence electrons of a calcium
atom? (1) 1s (2) 2s (3) 3s (4) 4s
3
33. The number of neutrons in 1H is (1) 1 (2) 2 (3) 3 (4) 4.

34–38 Base your answers on the ground state electron configura-


tions of four elements given below. In each case choose the
element that best fits the description. (1) 2-7 (2) 2-4 (3) 2-8-1
(4) 2-8-2

34. The element with the fewest valence electrons


35. The element with the greatest electronegativity
36. The element with the lowest ionization energy
37. This element contains no unpaired electrons.
38. This element contains five completely filled orbitals.

110 | Chapter 2: Atomic Structure


CONSTRUCTED RESPONSE

1. A certain element has an extremely low ionization energy.


Predict how this element would compare with most other
elements in:
(a) electronegativity
(b) number of principal energy levels
(c) number of valence electrons.
Explain each of your answers.
2. In the Periodic Table, you can see that Period 2 consists of
eight elements. (Li-Ne) The sublevels that fill in this period
are the 2s and the 2p. For Periods 3, 5, and 6, identify
(a) the number of elements in the period, and
(b) the sublevels that fill in the period.
3. Bohr’s theory of the atom contained the following assertions:
(a) Electrons move in fixed, circular orbits around the
nucleus.
(b) The energy of the electron is quantized.
(c) Electrons emit energy when they fall from higher to
lower energy levels.
Which of these assertions has been changed in modern atom-
ic theory? How has it been changed?
4. Based on the electron configurations given on the Periodic
Table in Appendix 5, which 4 elements in Groups 3 to 10
have no unpaired electrons?

CHEMISTRY CHALLENGE

The following questions will provide practice in answering SAT II-


type questions.
Use the Periodic Table in Appendix 5 to help you.

Chemistry Challenge | 111


1. The S2 ion has the same number of electrons as (1) Ne
(2) Na (3) Ca2 (4) K
2. Of the following ions, the one with the smallest ionic radius
is (1) O2 (2) F (3) N3 (4) Na
3. An ion with the electron configuration 1s22s22p63s23p6 has a
charge of 2. The number of protons in this ion is (1) 18
(2) 20 (3) 16 (4) 22
4. The sublevel filling in elements 39–48 is the (1) 3d (2) 4d
(3) 4ƒ (4) 5ƒ
5. How many unpaired electrons are there on an element with
the electron configuration [Ar]3d64s2? (1) 6 (2) 5 (3) 4
(4) 2
6. What is the next sublevel to fill after the 4d? (1) 4p (2) 3s
(3) 5p (4) 5s
7. As an atom gains electrons, its radius (1) decreases (2) increases
(3) remains the same
8. A V2 ion loses three electrons. The new ion formed would
have the symbol (1) V1 (2) V5 (3) Ca2 (4) Ca1
9. Which element in Period 4 has six unpaired electrons in the
ground state? (1) Cr (2) Mn (3) Fe (4) Ar
10. Elements that have low ionization energies (1) tend to have
small atomic radii (2) tend to have low electronegativities
(3) tend to form negative ions (4) tend to be found on the
right side of the Periodic Table.

112 | Chapter 2: Atomic Structure


Heisenberg Might Have Slept Here
Werner Heisenberg is known best for his “uncertainty principle,”
which says that there is no way we can measure with complete
certainty the behavior of a physical object. The uncertainty
principle helped Heisenberg win the Nobel Prize in 1932. In
Heisenberg’s case, though, the uncertainty principle applies to
his life as much as it does to his science.

Heisenberg headed the German atomic energy project dur-


ing World War II. His objective was to develop an atomic bomb
for Germany. If he had succeeded, the course of history might
have been changed. We are uncertain as to why the German
project failed. Some historians believe that Heisenberg deliber-
ately sabotaged the project to prevent Nazi Germany from
acquiring so powerful a weapon. Others insist that Heisenberg
simply miscalculated the amount of fissionable material needed
to build a nuclear weapon; as a loyal and patriotic German, he
would have built the bomb had he been able to. Heisenberg’s
biography, written by David Cassidy, is entitled Uncertainty: The
Life and Science of Werner Heisenberg.

Playwright Michael Frayn found the uncertainty surrounding


Heisenberg so fascinating that he wrote the play Copenhagen
about Heisenberg’s 1941 meeting with the Danish physicist Niels
Bohr. Before the war the two men had been good friends.
However, by 1941 Germany had invaded and occupied
Denmark, which strained their friendship. In the play, Frayn pre-
sents three versions of what might have happened during that
meeting. Copenhagen had successful runs both in London and
New York, and it has recently been made into a movie. The play-
wright believes that the uncertainty principle is as applicable to
human thinking as it is to the movement of electrons.

Once, while driving through New Jersey, I passed a car with


the bumper sticker that said, “Heisenberg Might Have Slept
Here.” I laughed out loud.

Heisenberg Might Have Slept Here | 113